As a girl, Elena was educated privately at home, her first years' education being supervised by her paternal grandmother, the formidable Catherine II of Russia. As any other royal of her time, the Grand Duchess' education was focused mainly on art, literature and music. Her real purpose in life, eventually, would be to marry well and provide her husband-to-be with children. Out of all her siblings, Elena was closest to her older sister Alexandra, whose life was shaped practically the same as was Elena's.

Elena's mother, Sophie Marie Dorothea of Württemberg (by now known as Maria Fyodorovna following her baptism in the Orthodox faith), turned out to be an excellent matchmaker. Although one of her daughters died as an infant, the rest married members of Europe's most important and prestigious royal houses.

In 1798 the situation in Europe was such that Russia decided for a closer military cooperation with Austria, supported by a consent to the marriage of Grand Duchess Alexandra Pavlovna with Archduke Joseph, Palatine of Hungary. At the same time, negotiations began on the marriage of Grand Duchess Elena Pavlovna with the heir of a small but politically profitable state, the Duchy of Mecklenburg-Schwerin. The negotiations went without any complications and ended successfully.

The day-of court records of 17 February 1799 wrote: arrived in St. Petersburg their Highnesses Princes Frederick and Carl of Mecklenburg-Schwerin. They received a set of rooms in the Marble Palace and where invited to the imperial table.

The formal betrothal between Grand Duchess Elena and the Hereditary Prince of Mecklenburg-Schwerin was celebrated on 5 May 1799. It was customary for European princesses to travel to their husband's homelands to wed; Russian Grand Duchesses were always the exception, as they were all married at home following tradition. On 23 October 1799 Elena Pavlovna and Friedrich Ludwig were married at the palace of Gatchina. Her sister Alexandra followed her example and married her fiancé in the same place one week later.

Grand Duchess Elena Pavlovna (now Hereditary Grand Duchess Elena) moved to Schwerin with her husband. There she was introduced to a whole new court, quite different from the opulence of Saint Petersburg. She was quite content with her married life and soon after the wedding she was with child. In September 1800 she gave birth to a son, Paul Friedrich, Grand Duke of Mecklenburg-Schwerin from 1837 till 1842, who was named so after his grandfathers, the Tsar of Russia and the Grand Duke of Mecklenburg-Schwerin.
The year 1801 had been especially hard for Elena, for she lost two close members of her family in just a few days. On 16 March her sister Alexandra died in Buda after giving birth to a daughter Alexandrine, who died a few days before. Just eight days later her father, the tsar, was assassinated. The following year Elena became pregnant again and in March 1803 produced a daughter whom they named Marie Louise after her grandmothers, the Dowager Tsarina and Duchess Louise of Mecklenburg-Schwerin.

In September 1803, Elena Pavlovna fell gravely ill and died suddenly on 24 September. She was buried with great sorrow in the Helena Paulovna Mausoleum in Ludwigslust which was named in her memory.[1] Several members of the Mecklenburg-Schwerin dynasty, including her husband's second and third wife, are buried there.

Elena's widower, Friedrich Ludwig, remarried in 1810 to Caroline Louise of Saxe-Weimar. They had a daughter, Princess Helene Luise Elisabeth (1814–1858), who married Ferdinand Philippe d’Orléans, Duke of Chartres (1810–1842), but Friedrich again became a widower in 1816. In 1818 he married Landgravine Auguste of Hesse-Homburg but he died the following year. He never became Grand Duke because his father outlived him, and he was succeeded by Elena Pavlovna's son, Paul Friedrich, in 1837.